Nanostructured NaAlO2 microspheres are produced from an aqueous solution, by a one-pot spray drying route. The obtained solids are composed of spherical aggregates of sodium aluminate with small crystallite size and strong surface basicity. This makes them highly active catalysts in the base-catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate. The new catalyst does not leach and is recyclable. NaAlO2 microspheres outcompete commercially available NaAlO2 as well as other basic catalysts in the usual reaction conditions, i.e. at relatively high reaction temperature. Remarkably, the new catalyst also catalyzes efficiently the room temperature synthesis of glycerol carbonate.